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P.G. Department of Chemistry, G. M. College, Sambalpur-768 004, Odisha, India E-mail : mahapatra.bipin@yahoo.com Department of Chemistry, Govt. College of Engineering, Kalahandi, Bhawanipatna, Odisha, India E-mail : ashishsbp_2008@yahoo.com Manuscript received 08 April 2015, revised 15 July 2015, accepted 31 July 2015 The new azodye ligand 4,4´-(1E,1´E)-biphenyl-4,4´-diylbis(diazene-2,1-diyl)bis(4-nitrophenol) (BPDBDADBP) and its complexes of the type [M2LCl2(H2O)6], {M = CoII, NiII, CuII} and [M´2LCl2(H2O)2], {M´ = ZnII, CdII, HgII} were synthesized. The ligand and the complexes were characterized by elemental analytical, conductivity measurement, magnetic moments (RT), IR, electronic spectra, ESR, NMR, TG, DTA and X-ray diffraction (powder pattern) spectra and theoretical (DFT/B3LYP) studies. The CoII and NiII complexes are found to be octahedral, CuII complexes are distorted octahedral and ZnII, CdII and HgII complexes are suggested to be tetrahedral stereochemistry. The thermal analysis data provided the kinetic parameters as order of decomposition reaction, activation energy and frequency factor. All theoretical calculations of the ligand and the CuII and ZnII complexes were made using GAUSSIAN 03 rev. A.01 programme package hybrid DFT/B3LYP hybrid functional level of theory with LANL2DZ basic set for copper and zinc atoms in gas phase and 6-31G(d,p) basic set for other atoms. The DFT study of the ligand and the complexes is used to calculate the bond length, bond angle, dihedral angle, HOMO, LUMO and dipole moment values. The calculated HOMO-LUMO energy gap shows that a charge transfer occurs within the molecule. The calculated value of zero point energy indicates that the stability of the metal complexes is greater than the ligand. The XRD data reveals that ZnII complex is found to have a monoclinic crystal system. |
